1. Technical Field
The present invention relates to a method for using ethylenediaminetetraacetic acid (EDTA) and unmodified TiO2 for the photocatalyic removal of selenium-containing materials from an aqueous solution in which EDTA is used as a hole scavenger and the method includes the use of artificial light, or solar radiation, photocatalysis for the removal of aqueous phase selenite and selenate species.
2. Description of the Related Art
The “background” description provided herein is for the purpose of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description which may not otherwise qualify as prior art at the time of filing, are neither expressly or impliedly admitted as prior art against the present invention.
Enhanced industrial practices such as mining, fossil fuel extraction/use, etc., mobilize an otherwise bound selenium species into a natural environment. For example, erosion of soils due to agricultural practices leads to increased selenium in ground and surface water (D. Wang, G. Alfthan, A. Aro, P. Lahermo, and P. Vaananen, The impact of selenium fertilisation on the distribution of selenium in rivers in Finland, Agric., Ecosys. Environ. 50 (1994), pp. 133-149-incorporated herein by reference in its entirety) whereas leaching from mining sites' soils/rocks also releases selenium species into natural waterways (J. Högberg and J. Alexander, Chapter 38—Selenium, in Handbook on the Toxicology of Metals, Gunnar F. Nordberg, Bruce A. Fowler, Monica Nordberg and Lars Friberg, Third Edition, Academic Press, Burlington, 2007, pp. 783-807; ATSDR, Toxicological profile for selenium, ATSDR, 2003; P. Zhang and D. L Sparks, Kinetics of selenate and selenite adsorption/desorption at the goethite/water interface, Environmental Science & Technology. 24 (1990), pp. 1848-1856—each incorporated herein by reference in its entirety). Furthermore, effluents from industries such as oil refineries & power plants and use of selenium based chemicals in several industrial processes, also discharge selenium into the natural environment. Though selenium is an essential micronutrient, a relatively thin margin exists between selenium amounts resulting in deficiency and toxicity and a significant exposure causes serious ecological concerns (U. Tinggi, Essentiality and Toxicity of Selenium and its Status in Australia: a Review, Toxic. Let. 137 (2003), pp. 103-110; J. O. Hall, Chapter 34—Selenium, in Veterinary Toxicology, C. G. Ramesh, Academic Press, Oxford, 2007, pp. 453-460; U. Tinggi, Selenium: its role as antioxidant in human health, Environ Health Prey. Med. 13 (2008), pp. 102-108; R. A. Sunde, Selenium”, in: Present Knowledge in Nutrition, Bowman, B. A. and Russell, 9th edition, R. M., ILSI Press, Washington, D.C., 2006, pp. 480-497; A. D. Lemly, Ecosystem recovery following selenium contamination in a freshwater reservoir, Ecotox. Environ. Safi 36 (1997), pp. 275-281; A. D. Lemly, Aquatic Hazard of Selenium pollution from Mountaintop Removal Coal Mining, Appalachian Cent. For the Econ. & the Environ. And the Sierra Club, 2009. Available at http://www.filonverde.org/images/informe_selenio_en_minas_a_cielo_abierto.pdf; R. L. J. P. Skorupa and L. A. Peltz, Areas Susceptible to Irrigation-Induced Selenium Contamination of Water and Biota in the Western United States, U.S. Dept. of the Interior, U.S. Geological Survey 1999. Available at http://pubs.usgs.gov/circ/circ1180/—each incorporated herein by reference in its entirety). The respective selenium drinking water and wastewater discharge standards are very stringent.
Typically selenium occurs in four natural oxidation states: i.e., elemental selenium (0), selenide (−2), selenite (+4) and selenate (+6) (F. Seby, M. Potin-Gautier, E. Giffaut, G. Borge and O. F. X. Donard, A Critical Review of Thermodynamic Data for Selenium Species at 25° C., Chem. Geo. 171 (2001), pp. 173-194—incorporated herein by reference in its entirety). Out of these selenite and selenate (inorganic oxyanion species) are the most dominant in the aqueous phase because of their high solubility and mobility. Selenate is most dominant because of its low adsorption on to naturally occurring surfaces and is not well retarded in the natural environment while selenite's mobility is mainly governed by adsorption/desorption processes occurring on to various solid surfaces such as metal oxyhydroxides (D. G. Barceloux, Selenium, J. Toxicol Clin Toxicol. 37 (1999): 145-172—incorporated herein by reference in its entirety). Several technologies including adsorption, reverse osmosis, nano-filtration, evaporation ponds, ferrous hydroxide treatment, biological processes, and constructed wetlands have been used for the above mentioned selenium oxyanions removal, with each of these methods having its own advantages and disadvantages (L. Twidwell, J. McCloskey, H. Joyce, E. Dahlgren, and A. Hadden, Removal of selenium oxyanions from mine waters utilizing elemental iron and galvanically coupled metals, In Innovations in Natural ResourceProcessing—Proceedings of the Jan. D. Miller Symposium; SSEMP, Draft technologies and management techniques to limit exposures to selenium, available at http://www.water.ca.gov/saltonsea/historicalcalendar/wg/03.04.2005/SeleniumMgmtTech.pdf—each incorporated herein by reference in its entirety). Titanium dioxide (TiO2) assisted photocatalytic degradation (PCD) which is an advanced treatment technology has also been widely studied for the removal of both organic and inorganic pollutants from contaminated water bodies (A. Fujishima, T. N. Rao and D. A. Tryk, Titanium dioxide photocatalysis, J. Photochem. Photobio. C: Photochem. Rev. 1 (2000): pp. 1-21; K. Hashimoto, H. Irie, and A. Fujishima, TiO2 photocatalysis: a historical overview and future prospects, AAPS Bulletin. 17 (2007), pp. 8269-8285—each incorporated herein by reference in its entirety). When feasible, the PCD process offers several advantages including minimum waste by-products, low operational temperature, use of a non-toxic and reusable photocatalyst, no specific chemical requirement, and possible use of sun light as an energy source.
Furthermore the Kingdom of Saudi Arabia (KSA) is fortunate to have an abundant year round supply of solar energy and KSA is one of the only few regions in world that receive the highest amount of solar radiation (World Solar Commission, World Solar Programme 1996-2005: Africa (ASP). Mechanisms of Implementation (An Outline), Prepared by the Secretariat of the World Solar Commission, (2001)—incorporated herein by reference in its entirety). Among many other uses, this virtually unlimited source of energy can be utilized for environmental cleanup as well. Use of solar radiation for several environmental applications including advanced wastewater treatment have also been reported for other locations (J. Blanco, S. Malato, P. Fernandez-Ibañez, D. Alarcon, W. Gernjak, and M. I. Maldonado, Review offeasible solar energy applications to water processes, Renewable and Sustainable Energy Reviews 13 (2009), pp. 1437-1445; Julian Blanco-Galvez, Pilar Fernández-Ibáñez and Sixto Malato-Rodríguez, Solar photocatalytic detoxification and disinfection of water: recent overview, J. Sol. Energy Eng. 129 (2006), pp. 4-15; Antonio E. Jimenez, Claudio A. Estrada, Alma D. Cota, and Alberto Román, Photocatalytic degradation of DBSNa using solar energy, Solar Energy Materials and Solar Cells 60 (2000), pp. 85-95; C. Karunakaran and R. Dhanalakshmi, Semiconductor-catalyzed degradation of phenols with sunlight, Solar Energy Materials and Solar Cells 92 (2008), pp. 1315-1321; S. Malato. P. Fernández-Ibáñez, M. I. Maldonado, J. Blanco, and W. Gernjak, Decontamination and disinfection of water by solar photocatalysis: Recent overview and trends, Catalysis Today 147 (2009), pp. 1-59; B. Neppolian, H. C. Choi, S. Sakthivel, B. Arabindoo, and V. Murugesan, Solar light induced and TiO2 assisted degradation of textile dye reactive blue 4, Chemosphere 46 (2002), pp. 1173-1181; S. S. Priya, S. Shanmuga M. Premalatha, and N. Anantharaman, Solar Photocatalytic Treatment of Phenolic Wastewater Potential, Challenges and Opportunites. Journal of Engineering and Applied Sciences, 3 (2008). pp. 36-41; M. Saquib, M. Abu Tariq, M. M. Hague, and M. Muneer, Photocatalytic degradation of disperse blue 1 using UV/TiO2/H2O2 process, Journal of Environmental Management 88 (2008), pp. 300-306; C. Sichel, P. Fernández-Ibañez, M. de Cara, and J. Tello, Lethal synergy of solar UV-radiation and H2O2 on wild Fusarium solani spores in distilled and natural well water,” Water Research 43 (2009), pp. 1841-1850—each incorporated herein by reference in its entirety). As mentioned above, one such advanced oxidation process (AOP) that can be used to treat industrial wastewaters includes solar radiation energized titanium dioxide (TiO2) assisted photocatalytic degradation process or TiO2-Photocatalysis (SPCD).
For example the SPCD technology has been widely studied in many regions around the globe (Detlef Bahnemann, Photocatalytic water treatment: solar energy applications, Solar Energy 77 (2004), pp. 445-459; Pilar Fernandez-Ibañez, Sixto Malato, and Octav Enea, Photoelectrochemical reactors for the solar decontamination of water, Catalysis Today 54 (1999), pp. 329-339; S. Malato, J. Blanco, C. Richter, B. Braun, and M. I. Maldonado, Enhancement of the rate of solar photocatalytic mineralization of organic pollutants by inorganic oxidizing species, Applied Catalysis B: Environmental 17 (1998), pp. 347-356; S. Malato, J. Blanco, C. Richter, B. Milow, and M. I. Maldonado, Solar photocatalytic mineralization of commercial pesticides: Methamidophos, Chemosphere 38 (1999), pp. 1145-1156; S. Malato, J. Caceres, A. Agiiera, M. Mezcua, D. Hernando, J. Vial, and A. R. Fernandez-Alba, Degradation of Imidacloprid in Water by Photo-Fenton and TiO2 Photocatalysis at a Solar Pilot Plant: A Comparative Study, Environmental Science & Technology 35 (2001), pp. 4359-4366; S. Malato, J. Blanco, A. Vidal, P. Fernandez, J. Caceres, P. Trincado, J. C. Oliveira, and M. Vincent, New large solar photocatalytic plant: set-up and preliminary results, Chemosphere 47 (2002), pp. 235-240; M. Mehos, C. Turchi, J. Pacheco, A. J. Boegel, T. Merrill, and R. Stanley, Pilot-scale study of the solar detoxification of VOC-contaminated groundwater, Technical Report submitted at American Institute of Chemical Engineers (AIChE) summer national meeting, Minneapolis, Minn. (United States) (1992); J. E. Pacheco and C. E. Tyner, Enhancement of processes for solar photocatalytic detoxification of water, ASME international solar energy conference, Miami, Fla. (USA) (1990); W. Scott Rader, Ljiljana Solujic, Emil B. Milosavljevic, James L. Hendrix, and John H. Nelson, Sunlight-induced photochemistry of aqueous solutions of hexacyanoferrate(II) and -(III) ions, Environmental Science & Technology 27 (1993), pp. 1875-1879; Didier Robert and Sixto Malato, Solar photocatalysis: a clean process for water detoxification, Science of The Total Environment 291 (2002), pp. 85-97; Manuel Romero, Julián Blanco, Benigno Sanchez, Alfonso Vidal, Malato Sixto, Ana I. Cardona, and Elisa Garcia, Solar photocatalytic degradation of water and air pollutants: challenges and perspectives, Solar Energy 66 (1999), pp. 169-182; Julian Blanco Galvez and Sixto Malato Rodriguez, Solar detoxification in Renewable energy series, edited by Julian Blanco Galvez and Sixto Malato Rodriguez, UNESCO (2003); Susana Flores Villanueva and Susana Silva Martínez, TiO2-assisted degradation of acid orange 7 textile dye under solar light, Solar Energy Materials and Solar Cells 91 (2007), pp. 1492-1495; Archis A. Yawalkar, Dhananjay S. Bhatkhande, Vishwas G. Pangarkar, and Anthony ACM Beenackers, Solar-assisted photochemical and photocatalytic degradation of phenol, Journal of Chemical Technology & Biotechnology 76 (2001), pp. 363-370—each incorporated herein by reference in its entirety). The SPCD technology incorporates use of the catalyst TiO2 and solar UV light to degrade the target pollutant. Use of solar radiation instead of artificial UV light lamps during the SPCD advanced oxidation process is expected to be efficient and economical in regions that are rich in solar energy such as KSA. Hence the abundant solar energy natural resource of Kingdom of Saudi Arabia offers an opportunity to utilize it for respective environmental applications. Considering the concerns related with selenium pollution an appropriate treatment of respective streams is required to mitigate those adverse concerns and also to meet the selenium discharge limits.
The essential or toxic character of selenium depends on its concentration in food, water and other living organisms, as well as its chemical speciation and distribution in soils, wetlands and aqueous ecosystems. Atmospheric deposition, surface runoff, and subsurface drainage account for selenium contamination in surface water. Use of fossil fuels also introduces selenium species into natural environment.
When present, Se (IV), selenite and Se (VI), selenate are typical selenium species in respective water bodies.
Selenium can occur with and replaces sulfur because of the similarities in their chemical properties. Selenium combines with metals and many nonmetals directly or in aqueous solution. (Ana Benedicto, Tiziana Missana, and Claude Degueldre, Predictions of TiO2 driven migration of Se(IV) based on an integrated study of TiO2 colloid stability and Se(IV) surface adsorption, Science of the Total Environment 449 (2013), pp. 214-222—incorporated herein by reference in its entirety).
In the 13th century, Marco Polo noticed the presence of certain poisonous plants that had serious effects on the beasts that consume it in the province of Shanxi. This description made before the discovery of selenium, is probably a symptom of its toxicity (Helina Hartikainen, Biogeochemistry of selenium and its impact on food chain quality and human health, J. of Trace Elements in Medicine and Biology 18 (2005) pp. 309-318—incorporated herein by reference in its entirety).
Selenium poisoning clinical signs include hair loss, fingernails changes and brittleness, gastrointestinal disturbances, skin rash, garlic breath, and abnormal functioning of the nervous system (Miguel Navarro-Alarcon and Carmen Cabrera-Vique, Selenium in food and the human body: A review, Sc. of the Total Env. 400 (2008) pp. 115-141—incorporated herein by reference in its entirety).
The health effects are recorded on humans as a result of high selenium status (M. P. Rayman, Selenium and human health, The Lancet 379 (2000) pp. 1256-1268—incorporated herein by reference in its entirety).
Maximum contaminant levels for selenium have been made by different authorities based on the extent of the results of some field studies. MCLs for WHO, Health Canada and Australia are set at 0.01 mg/L while USEPA currently has MCLs of 0.05 mg/L (Health Canada, Environmental and workplace health: Selenium, available at http://www.hc-sc.gc.ca/ewh-semt/pubs/water-eau/selenium/index-eng.php; WHO, Selenium in drinking-water, World Health Organization (2011); NPI, Selenium & compounds: Health effects, Commonwealth of Australia—each incorporated herein by reference in its entirety). However, a more stringent freshwater discharge standard of 5 μg/L is set up by EPA (USEPA, National recommended water quality criteria, (1995)—incorporated herein by reference in its entirety).
PCD Process
TiO2 used in the photocatalytic degradation (PCD) process is an n-type semiconductor and both the anatase and rutile crystal forms of TiO2 have been widely used in the PCD studies. Furthermore TiO2 possesses a void energy region also known as band gap (BG) between its valence band (VB) and conduction band (CB), extending from the top of the electronfilled VB to the bottom of the vacant CB. Thus when a TiO2 particle is exposed to a UV light source with energy hν equivalent to or higher than the bandgap energy (BGE) the VB electrons are transferred to CB thus creating an electron-hole pair (e−/h+) as given in reaction 2-1:TiO2+hν→e−+h+  (2-1)e−-h+ recombination can occur in the bulk and/or on the surface (Equation 2-2). When the h+ and e− are successfully transferred to the TiO2 surface, the h+ can oxidize an electron donor such as an organic compound (Equation 2-3) while the e− can reduce an electron acceptor e.g., selenite (Equation 2-4) and selenate (Equation 2-5).e−+h+→heat  (2-2)organic compound+h+→oxidized products  (2-3)SeO32−+6H++4e−Se0+3H2O  (2-4)SeO42−+8H++6e−Se0+4H2O  (2-5)
Furthermore reactions 2-6 and 2-7 are also typically used to represent the naked-TiO2 surface in contact with the water molecules (W. Stumm, Aquatic Surface Chemistry: Chemical Processes at the Particle-Water Interface, Wiley, (1987)—incorporated herein by reference in its entirety):Ti—OH2+Ti—OH+H+  (2-6)Ti—OHTi—O−+H  (2-7)
The h+ species produced in reaction 2-1 is electron deficient and hence reacts with an adsorbed hydroxyl molecule OH− on the TiO2 surface to produce an OH. radical (Reaction 2-8):Ti—OH−+h+→Ti—OH  (2-8)
The OH radicals are powerful and non-selective oxidants that can typically simultaneously remove both organic and inorganic pollutants from the concerned wastewaters. However direct oxidation of organic compounds by holes/h+ has been reported as well. Furthermore the electrons/e− produced in Equation 2-1 could be consumed by a suitable electron acceptor such as O2 or a metal species. In case of selenite or selenate, the e species could possibly be utilized for their reduction and consequent removal from the aqueous phase (Equations 2-4 and 2-5).
An earlier work on TiO2 photocatalytic reduction of selenium oxyanions was carried out by E. Kikuchi (E. Kikuchi, S. Itou, M. Kobayasi and H. Sakamoto, Reduction and removal of selenate ion by TiO2 photo-catalyst, J. NIRE. 6 (1997), pp. 173-177—incorporated herein by reference in its entirety). Since then these systems have been examined by several other groups (S. Sanuki, T. Kojima, K. Arai, S. Nagaoka and H. Majima, photocatalytic reduction of selenate and selenite solutions using TiO2 powders, Met. Mat. Trans. B. 30 (1999), pp. 15-20; S. Sanuki, K. Shako, S. Nagaoka and H. Majima, Photocatalytic reduction of Se ions using suspended anatase powders, Mat. Trans., JIM. 41 (2000), pp. 799-805; T. Tan, D. Beydoun and R. Amal, Effect of organic holes scavengers on the photocatalytic reduction of selenium anions, J. Photochem. Photobio. A: Chem. 159 (2003), pp. 273-280—each incorporated herein by reference in its entirety). Many of these studies have also investigated the role of hole (h+) scavengers such as formic acid during TiO2 assisted photocatalytic reduction of selenite and selenate and report significant removal of selenium contamination from the aqueous phase (V. N. H. Nguyen, R. Amal and D. Beydoun, Photocatalytic reduction of selenium ions using different TiO2 photocatalysts, Chem. Eng. Sci. 60 (2005), pp. 5759-5769; V. N. H. Nguyen, D. Beydoun and R. Amal, Photocatalytic reduction of selenite and selenate using TiO2 photocatalysts, Journal of Photochem. and Photobio. A: Chem. 171 (2005), pp. 113-120—each incorporated herein by reference in its entirety). Recently Aman et al. (N. Aman, T. Mishra, J. Hait and R. K. Jana, Simultaneous photoreductive removal of copper (II) and selenium (IV) under visible light over spherical binary oxide photocatalyst, J. Haz. Mater. 186 (2011), pp. 360-366—incorporated herein by reference in its entirety) also reported using a modified Ti—Zr based photocatalyst and EDTA (as a hole scavenger) for selenite/selenate removal from the aqueous phase. Nevertheless the role of EDTA as a hole scavenger for the removal of respective selenium species using unmodified TiO2 photocatalysis, has not been investigated. Aman et al. report on simultaneous photo-reductive removal of copper (II) and selenium (IV) using Ti, Ti—Zr, and Ti—Si binary oxide photocatalysts and visible light under a varying set of conditions including single and mixed copper and selenium systems. The prepared catalysts had high specific surface area and were mesoporous. TiZr-10 was noted to be the best photocatalyst. Also pH 3 was noted to be the optimum and yielded highest photocatalytic selenite reduction in a mixed solution. Out of many hole scavengers tested, formic acid and ethylenediaminetetraacetic acid (EDTA) were best for the reduction of selenium oxyanions. The h+ species produced in Equation 2-1 are consumed by the h+ scavengers, resulting in reduced e−/h+ recombination (Equation 2-2) and thus leaving more e− species for reduction of selenite (analogous to Equation 2-4). Furthermore for single pollutant system, formic acid yielded better results for Se(IV) reduction whereas EDTA was noted to be better for Cu(II) reduction. However for mixed systems, both formic acid and EDTA showed better metal reduction results and the copper selenide was noted to be deposited at the catalyst surface. Nguyen et al. noted that in the presence of formic acid as a hole scavenger both selenite and selenate were photoreduced to Se(0) in illuminated TiO2 suspensions. Findings from the UV-Vis reflectance indicated that compared to pure TiO2 the Se/TiO2 sample had a red-shift; an additional absorbance peak at approx. 680 nm was assigned to Se(0). The elemental selenium species accumulated on the TiO2 particles either in a particulate or film form. It was proposed that the formation of Se(0) particles was due to a chemical reaction between Se(IV) and Se2− whereas a direct reduction of Se(IV) by the conduction band electrons (TiO2) resulted in the formation of a Se(0) film. The Se2− species was suggested to result either from photoreduction of Se(0) or because of reduction of Se(IV). Shi et al. who investigated selenite sorption on TiO2 indicated that selenite sorption is a function of pH and its kinetics can be given as a pseudo-second-order model (K. Shi, X. Wang, Z. Guo, S. Wang, and W. Wu, Se(IV) sorption on TiO2: Sorption kinetics and surface complexation modeling, Colloids and Surf. A: Physicochem. and Eng. Asp. 349 (2009), pp. 90-95—incorporated herein by reference in its entirety). The authors also employed the constant capacitance model to predict selenite sorption on to TiO2. Tan et al. also investigated the reduction of selenium oxyanions (selenite and selenate) to elemental selenium using TiO2 assisted photocatalysis. The authors employed several hole scavenging agents including acetic acid, methanol, ethanol, salicylic acid, formic acid, and sucrose. Significant reduction of selenium oxyanions was possible using ethanol, formic acid, and methanol, with following order: formic acid >methanol >ethanol. This high capability of formic acid to reduce selenium oxyanions was explained based on its effective mineralization, formation reducing radicals, and adsorption of both the selenium species and formic acid onto TiO2. Insignificant adsorption of ethanol and methanol was explained based on competitive selenium species adsorption on to the TiO2 surface, resulting in reduced role of hole scavenger ethanol and methanol resulting in their reduced efficiency. For the formic acid case the optimum pH for selenium oxyanions photoreduction was 3.5-4. For methanol and ethanol the optimum pH value was 2.2.
Tan et al. investigated the PCD initiated reduction of selenate using TiO2 and Ag-loaded TiO2 and formic acid; selenate was successfully reduced to elemental selenium species employing the said photocatalysts and hole scavenger. The formation of Se2− followed H2Se formation using pure TiO2 whereas using Ag-loaded TiO2 photocatalyst H2Se and selenate reduction were noted to occur in parallel. Also pH 3.5 was noted to be optimum for reduction of selenate using 0.5% Ag loading. This high efficiency was explained based on electronic changes from TiO2—Ag—Se interaction and decreased e−/h+ recombination. In another study, Tan et al. report that the adsorption of formate and selenate onto TiO2 surface is a prerequisite for selenate reduction to elemental selenium which could further be reduced to H2Se (after selenate reduction to elemental form) (T. T. Y. Tan, and D. Beydoun, Photocatalytic reduction of Se(VI) in aqueous solutions in UV/TiO2 system: Importance of optimum ratio of reactants on TiO2 surface, J. Mol. Cat. A: Chem. 202 (2003), pp. 73-85—incorporated herein by reference in its entirety). The authors also report for optimum selenate reduction, a 3:1 formate:selenate ratio (on to TiO2 surface). This ratio could be maintained by controlling factors such as concentration of respective species and the aqueous phase pH. Also the noted 3:1 of formate:selenate ratio (on to TiO2 surface) strongly co-related with the stoichiometric ratio of 3 moles of formic acid to 1 mole of selenate for effective reduction. Tan et al. described selenate reduction rates in presence of formic acid employing Langmuir-Hinshelwood competitive adsorption models for selenate and formate ions onto TiO2 surface (T. T. Y. Tan, and D. Beydoun, Photocatalytic reduction of Se(VI) in aqueous solutions in UV/TiO2 system: Kinetic modeling and reaction mechanism, J. Phy. Chem. B. 107 (2003), pp. 4296-4303—incorporated herein by reference in its entirety). The respective models allowed for the modeling of formic acid and selenate adsorption on to TiO2. Furthermore a 3:1 formate:selenate ratio (on to TiO2 surface) was also obtained using the kinetic modeling exercise.
Zhang et al. also investigated sorption of selenium species on to TiO2 (L. Zhang, N. Liu, L. Yang, and Q. Lin, Sorption behavior of nano-TiO2 for the removal of selenium ions from aqueous solution, J. Haz. Mater. 170 (2009), pp. 1197-1203—incorporated herein by reference in its entirety). The maximum sorption was noted at pH 2-6. Also the sorption reached equilibrium within 5 min. The adsorption could be described both by boundary layer diffusion and intra-particle diffusion. Furthermore the adsorption kinetics results showed a second order kinetic model and the Langmuir adsorption isotherm was useful in modeling the respective findings.
Though many solar photocatalytic degradation (SPCD) studies have been reported on several aqueous phase pollution control issues, removal of selenite and selenate using SPCD process (using naked TiO2 and EDTA) has not been investigated. Augugliaro et al. studied cyanide degradation employing the TiO2 assisted photocatalysis using sun light as the energy source (V. Augugliaro, J. Blanco Gálvez, J. Cáceres Vázquez, E. Garcia López, V. Loddo, M. J. López Muñoz, S. Malato Rodriguez, G. Marci, L. Palmisano, M. Schiavello, and J. Soria Ruiz, Photocatalytic oxidation of cyanide in aqueous TiO2 suspensions irradiated by sunlight in mild and strong oxidant conditions, Catalysis Today 54 (199), pp. 245-253—incorporated herein by reference in its entirety). The authors report successful degradation of cyanide with nitrite, nitrate, cyanate, and carbonate as the reaction end products. In mixed systems containing both cyanide and phenol, the overall cyanide degradation efficiency decreased. Banu et al. investigated treatment of dairy wastewater by using a hybrid of biological and SPCD technologies (J. Rajesh Banu, S. Anandan, S. Kaliappan, and Ick-Tae Yeom, Treatment of dairy wastewater using anaerobic and solar photocatalytic methods, Solar Energy 82 (2008), pp. 812-819—incorporated herein by reference in its entirety). Using only biological treatment the authors noted about 84% reduction in the chemical oxygen demand (COD) value of respective wastewater. However an integration of biological and solar photocatalytic degradation processes caused 95% COD removal from the dairy wastewater. Choi et al. who studied degradation of several aqueous phase polychlorinated dibenzo-p-dioxins (PCDDs), report good removal of octa-chlorinated dibenzo-p-dioxin using the SPCD process (Wonyong Choi, Soo Jin Hong, Yoon-Seok Chang, and Youngmin Cho, Photocatalytic Degradation of Polychlorinated Dibenzo-p-dioxins on TiO2 Film under UV or Solar Light Irradiation, Environmental Science & Technology 34 (2000), pp. 48104815—incorporated herein by reference in its entirety). Furthermore the SPCD process was noted to be as effective as a 200 W mercury lamp for the respective application.
Cho et al. studied ex-situ treatment of petroleum contaminated groundwater at a gas station site using the solar radiation energized PCD process (Il-Hyoung Cho, Lee-Hyung Kim, Kyung-Duk Zoh, Jae-Hong Park, and Hyun-Yong Kim, Solar photocatalytic degradation of groundwater contaminated with petroleum hydrocarbons, Environmental Progress 25 (2006), pp. 99-109—incorporated herein by reference in its entirety). The authors report more than 70% reduction in the total petroleum hydrocarbons and BTEX compounds (benzene, toluene, ethylbenzene, xylene). Curco et al. report notable phenol removal using the SPCD technology that also showed linear dependence on the square root of photonic flow entering the wastewater treatment reactor (D. Curcó, S. Malato, J. Blanco, J. Giménez, and P. Marco, Photocatalytic degradation of phenol: Comparison between pilot-plant-scale and laboratory results,” Solar Energy 56 (1996), pp. 387-400—incorporated herein by reference in its entirety). Furthermore the phenol degradation was noted to be of first order with respect to its concentration.
Giménez et al. report similar observations for aqueous phase phenol removal using the SPCD process (Jaime Giménez, David Curcó, and Pilar Marco, Reactor modelling in the photocatalytic oxidation of wastewater, Water Science and Technology 35 (1997), pp. 207-213—incorporated herein by reference in its entirety).
Dias and Azevedo also report SPCD initiated removal of three commercially used acid dyes from the aqueous phase (M. G. Dias and E. B. Azevedo, Photocatalytic Decolorization of Commercial Acid Dyes using Solar Irradiation, Water Air Soil Pollut. 204 (2009), pp. 79-87—incorporated herein by reference in its entirety). Though direct photolysis of respective wastewater sample was effective only for one pollutant, the use of TiO2 mediated solar PCD technology caused removal of all dyes with acceptable reaction rates. The reaction rates for the three studied dyes were in the following order: Acid Red 51>Acid Yellow 23>Acid Blue 9. More than 99% mineralization was also noted within 120 min of reaction time.
Huang report notable silver ions removal from the aqueous phase using the SPCD process (Min Huang, Erwin Tso, Abhaya K. Datye, Michael R. Prairie, and Bertha M. Stange, Removal of Silver in Photographic Processing Waste by TiO2-Based Photocatalysis, Environmental Science & Technology 30 (1996), pp. 3084-3088—incorporated herein by reference in its entirety).
Jiménez et al. noted about 94% removal of a widely used surfactant, i.e., sodium dodecylbenzene sulfonate (DBSNa), using the solar PCD process. The use of an additional oxidant, i.e., H2O2, during the PCD process, caused complete degradation of DBSNa.
Kumara et al. also report complete removal of phenol and methyl violet from aqueous phase using the solar irradiated PCD process (G. R. R. A. Kumara, F. M. Sultanbawa, V. P. S. Perera, I. R. M. Kottegoda, and K. Tennakone, Continuous flow photochemical reactor for solar decontamination of water using immobilized TiO2,” Solar Energy Materials and Solar Cells 58 (1999), pp. 167-171—incorporated herein by reference in its entirety). However phenol degradation was noted to be faster than methyl violet. The authors also report complete removal of reaction intermediates as well.
Kuo and Ho investigated solar PCD of methylene blue contaiminated water (W. S. Kuo and P. H. Ho, Solar photocatalytic decolorization of methylene blue in water,” Chemosphere 45 (2001), pp. 77-83—incorporated herein by reference in its entirety). The authors report that employing solar radiation (in the absence of TiO2) only up to 50% color removal transpired. Near complete color removal occurred with the addition of TiO2 to the same reactor system. The de-colorization efficiency was higher (near twice) using solar radiation than the artificial UV light source. Such a phenomenon was ascribed to higher excitation of target dye by the visible wave length portion of solar light, which was lower in the artificial UV light source.
Malato et al. report significant increase in solar initiated PCD of pentachlorophenol in presence of peroxydisulphate. Malato et al. studied large scale solar photocatalytic degradation reactors for the degradation of several aqueous phase pesticides. The authors report significant increase in the degradation and mineralization of target pollutants in the presence of peroxydisulphate. This modification is of great practical significance as higher solar PCD reaction rate using peroxydisulphate means an overall smaller reactor size and in turn reduced overall footprint requirements for real life solar PCD applications. Malato et al. noted successful removal of imidacloprid (which is a widely used insecticide in the agricultural areas of Mediterranean region) using solar PCD. The authors report about 95% substrate and TOC removal within 450 min of reaction time. Oxalate, formate and acetate were reported to be the intermediates. Malato et al. who investigated use of a pilot scale solar assisted photocatalysis for the destruction of aqueous phase cyanide noted significant target pollutant removal. Removal of high initial cyanide concentration (1000 mg/L) was also stated to be degraded completely using the solar PCD system. It was suggested that complete mineralization of cyanide would transpire with end product nitrates containing most N-initial.
Marques et al. noted successful treatment of aqueous phase atrazine and also of an olive oil industry's wastewater using the solar PCD process in the presence of sodium persulfate (P. A. S. S. Marques, M. F. Rosa, F. Mendes, M. Collares Pereira, J. Blanco, and S. Malato, Wastewater detoxification of organic and inorganic toxic compounds with solar collectors, Desalination 108 (1997), pp. 213-220—incorporated herein by reference in its entirety). Significant total organic carbon removal was also observed indicating mineralization of the said waste streams and confirming that no possible toxic reaction intermediates are left behind. Nagaveni et al. also report significant phenol removal from the aqueous phase using sunlight energized TiO2 photocatalysis process (K. Nagaveni, G. Sivalingam, M. S. Hegde, and Giridhar Madras, Photocatalytic Degradation of Organic Compounds over Combustion-Synthesized Nano-TiO2, Environmental Science & Technology 38 (2004), pp. 1600-1604—incorporated herein by reference in its entirety). Use of specific combustion TiO2 that was prepared using a special technique yielded catalyst that was very effective in removing phenol from the aqueous phase, and the results were comparable for both artificial and sun radiation experiments.
Neppolian et al. studied SPCD initiated removal of aqueous phase textile dye reactive blue 4. Using solar energy and TiO2, the target pollutant was mineralized within 24 h. The results showed that the dye molecules were completely degraded to CO2, SO2, NO3−, NH4+, and H2O. Furthermore, quick removal of reaction intermediates was observed in the presence of hydrogen peroxide during the PCD process.
Pacheco et al. investigated the wastewater flow rates (for the SPCD reactor) that yield about 95% trichloroethylene removal for different locations across the U.S (J. Pacheco, M. Prairie, and L. Yellowhorse, Photocatalytic destruction of chlorinated solvents with solar energy (1990)—incorporated herein by reference in its entirety). It was noted that states such as New Mexico and Texas that receive higher amount of solar energy yield highest flow rates. Furthermore at any given location significantly higher wastewater flow was processed during the months of June and July as compared to the yearly-average flow rates. The study also showed highest trichloroethylene removal during noon time for different seasons (because of higher light intensity received at that time). These trends are consistent with the artificial UV light PCD findings.
For example Wei and Wan who studied the PCD of phenol report much lower phenol removal at low light intensities (Io) whereas with an increase in the light intensity from 30% to 77% (of maximum light intensity) a sharp increase in phenol removal was observed (Tsong Yang Wei and Chi Chao Wan, Heterogeneous photocatalytic oxidation of phenol with titanium dioxide powders, Industrial & Engineering Chemistry Research 30 (1991), pp. 1293-1300—incorporated herein by reference in its entirety).
Peterson et al. (1991) also report that at higher light intensity values, the PCD rate would be directly proportional to the Io1/2 while at low light intensities PCD rate would be a linear function of Io (Peterson, M. W., Turner, J. A., and Nozik, A. J., Mechanistic studies of the photocatalytic behavior of TiO2 particles in a photoelectrochemical slurry cell and the relevance to photodetoxification reactions. J. Phys. Chem. 95 (1991), pp. 221-225—incorporated herein by reference in its entirety). Sichel et al. investigated water disinfection using solar irradiation and a TiO2 catalyst (C. Sichel, J. Tello, M. de Cara, and P. Fernández-Ibáñez, Effect of UV solar intensity and dose on the photocatalytic disinfection of bacteria and fungi, Catalysis Today 129 (2007), pp. 152-160—incorporated herein by reference in its entirety). The experiments were performed with different illuminated reactor surfaces, in different seasons of the year, and under changing weather conditions. The findings indicate that SPCD process initiated disinfection is more susceptible to changes in solar irradiation and transpired only at increased sun light intensities.
Villaneuva and Martinez studied solar radiation energized photocatalytic degradation of aqueous phase acid orange 7 (AO7) (Susana Flores Villanueva and Susana Silva Martínez, TiO2-assisted degradation of acid orange 7 textile dye under solar light, Solar Energy Materials and Solar Cells 91 (2007), pp. 1492-1495—incorporated herein by reference in its entirety). The authors report approx. 85% color removal from an AO7 solution in 2 h reaction time. Faster color removal was noted at acidic pH. However the quantification of AO7 mineralization employing the chemical oxygen demand (COD) test indicated insignificant COD reduction. Nevertheless, more than 70% COD removal transpired upon use of persulphate along with TiO2 and solar radiation. Wang investigated PCD of eight commercial dyes using TiO2 assisted photocatalysis and solar irradiation (Yizhong Wang, Solar photocatalytic degradation of eight commercial dyes in TiO2 suspension, Water Research 34 (2000), 990-994—incorporated herein by reference in its entirety). The findings indicate that the target dyes could be degraded and mineralized to end products including chloride and sulfate.
Wei et al. studied disinfection of E. coli contaminated water using PCD initiated by UV-visible light with wavelength higher than 380 nm (Chang Wei, Wen Yuan Lin, Zulkarnain Zainal, Nathan E. Williams, Kai Zhu, Andrew P. Kruzic, Russell L. Smith, and Krishnan Rajeshwar, Bactericidal Activity of TiO2 Photocatalyst in Aqueous Media: Toward a Solar-Assisted Water Disinfection System, Environmental Science & Technology 28 (1994), pp. 934-938—incorporated herein by reference in its entirety). The authors report significant bacterial kill with the reaction rate following first order kinetics. The kinetic analysis indicated a pseudo first order kinetics with respect to the initial concentration of methylene blue as per the Langmuir-Hinshelwood model. The total organic carbon (TOC) removal showed two distinct regions, i.e., an initial pseudo first order kinetics that was noted till full color removal was followed by a slower TOC removal.
Furthermore continuous supply of oxygen gas during the SPCD process did not show any significant effect on the overall process efficiency as compared to an ‘open to air’ study. Zhang et al. studied removal of methylene blue using the solar PCD process (Tianyong Zhang, Toshiyu ki Oyama, Satoshi Horikoshi, Hisao Hidaka, Jincai Zhao, and Nick Serpone, Photocatalyzed N-demethylation and degradation of methylene blue in titania dispersions exposed to concentrated sunlight, Solar Energy Materials and Solar Cells 73 (2002), pp. 287-303—incorporated herein by reference in its entirety). The authors observed notable removal of target pollutant under a varying set of conditions.
It is evident from the above that the removal of selenite and selenate using UV-lamp energized pure TiO2 photocatalysis along with hole scavenger EDTA has not been studied. Furthermore use of solar energized TiO2 photocatalytic degradation (SPCD) process to treat wastewater streams containing selenite and selenate species, has also not been explored. Hence the main goal of this present disclosure is to study removal of selenite and selenate species using TiO2 assisted advanced oxidation process using both UV-lamp and solar energy as the light energy source.